Substituted 4,7-methanoindenes perfume compositions

ABSTRACT

PERFUME COMPOSITION CONTAINING AS AN OLFACTORY INGREDIENT A HEXAHYDRO OR OCTAHYDRO-4,7-METHANOINDENE SUBSTITUTED IN THE 5 OR 6 POSITION WITH A CARBOXYLATE OF AN ALPHA, BETA-UNSATURATED MONOCARBOXYLIC ACID.

United States Patent Olhce 3,598,745 Patented Aug. 10, 1971 3,598,745 SUBSTITUTED 4,7-METHANOINDENES PERFUME COMPOSITIONS Morris Dunkel, Paramus, N.J., assignor to Universal Oil Products Company, Des Plaines, Ill.

No Drawing. Original application Dec. 16, 1965, Ser. No. 514,373. Divided and this application Oct. 31, 1968, Ser. N 0. 772,409

Int. Cl. Cllb 9/00; A61k 1/00 US. Cl. 252-522 4 Claims ABSTRACT OF THE DISCLOSURE Perfume composition containing as an olfactory ingredient a hexahydro or octahydro-4,7-methanoindene substituted in the or 6 position with a carboxylate of an alpha, beta-unsaturated monocarboxylic acid.

CROSS REFERENCE TO RELATED APPLICATIONS This is a division of application Ser. No. 514,373, filed Dec. 16, 1965, which is now abandoned.

DESCRIPTION OF THE INVENTION This invention relates to perfume compositions containing a particularly substituted polyhydro-4,7-methanoindene.

Particularly substituted 4,7-methanoindenes of this invention have the following structural formulae:

wherein R R and R taken independently of each other, is a member selected from the group consisting of hydrogen and an alkyl radical and n is an integer of zero and one; provided, that for the carbon atom in the 5 or 6 position which is substituted with the substituent isomers from each other and for this reason it is intended that both isomeric compounds as well as mixtures thereof be encompassed Within this invention by describing the hexahydromethanoindene in this specification and appended claims as hexahydromethanoindene substituted in one of the 5 and 6 positions with the above suhstituent. No comparable problem exists for the octahydromethanoindenes of this invention illustrated as Formula 11 above, inasmuch as there is no double bond in the cyclopentane portion of the molecule and the positions 5 and 6 are accordingly chemically equivalent. For this reason, the octahydromethanoindene is described in this specifica tion and appended claims as being substituted with the substituent in the 5 position. It should be understood, however, that this nomenclature for the octahydromethanoindene is for convenience only inasmuch as for this rmethanoindene the positions 5 and 6 are chemically identical. Both the octahydro and hexahydromethanoindenes of this invention also exist in the exo and endo forms and it is intended that all of these isomeric compounds be encompassed Within this invention.

The novel 4,7-methanoindenes of this invention find wide utility in the chemical field and are especially useful as perfume materials due to their highly pleasant odoriferous nature. Of considerable significance in this respect is the fact that certain of these compounds, and particularly the hexahydromethanoindenes, possess a strong woody odor which has wide application in perfumery.

Accordingly, it is an object of this invention to provide perfume compositions containing these 4,7-methanoindenes as olfactory ingredients.

The 4,7-methanoindenes of this invention having the above general structures I and II are prepared, in general, according to the process of this invention by reacting the corresponding hydroxy substituted methanoindene with a reactant selected from the group consisting of (III) and R1C=CC-Y t) (IV) wherein R R and R have the same meaning as above, Y is a halogen and X is a member selected from the group consisting of hydrogen or an alkyl radical. Examples of these reactants which may be used in the process of this invention include acids, that is Where X in Formula III above is hydrogen, such as acrylic acid, methacrylic acid, alpha-ethyl acrylic acid, alpha, beta-dimethyl acrylic acid, alpha, beta-diethyl acrylic acid, crotonic acid, senecioic acid, alpha, beta, beta-trimethyl acrylic acid, or beta, beta-diethyl acrylic acid; esters, that is where X in Formula III above is an alkyl radical and preferably a lower alkyl radical, such as methyl, ethyl, propyl, butyl, or amyl esters of the above acids; or acid halides, that is where Y in the Formula IV above is halogen and preferably a chloride, such as acrylyl chloride, rnethacrylyl chloride, alpha-ethyl acrylyl chloride, alpha, beta-dimethyl acrylyl chloride, crotonoyl chloride, or senecioyl chloride.

The hydroxy substituted 4,7-methanoindene reacted with the reactants, illustrated by Formulae III and IV above, to prepare the substituted hexahydromethanoindenes of this invention, represented by Formula I above, may be readily obtained from the dimer of cyclopentadiene,- 3a,4,7,7a-tetrahydro-4,7-methanoindene, by reacting such tetrahydromethanoindene with aqueous sulfuric acid to produce 3a,4,5,6,7,7a-hexahydro 4,7 methanoindenol substituted in one of the and 6 positions with the hydroxy group. The hydroxy substituted 4,7-methanoindene reacted with the reactants to prepare the substituted octahydromethanoindenes of this invention, represented by Formula II above, may be readily obtained by mildly hydrogenating the hydroxy substituted hexahydromethanoindene prepared as above to produce 5-hydroxy-2,3,3a,4,5,6,7,7aoctahydro-4,7-methanindene. Examples of the substituted 4,7-methanoindenes of this invention prepared by reacting the corresponding hydroxy substituted methanoindene with one of the reactants illustrated by the above Formulae III and IV and include: 3a,4,5,6,7,7a hexahydro-4,7 methanoindene substituted in one of the 5 and 6 positions with acrylyloxy; 3 a,4,5,6,7,7a-hexahydro-4,7-methanoindene substituted in one of the 5 and 6 positions with alpha, beta-dimethyl acrylyloxy; 3a,4,5,6,7,7a-hexahydro- 4,7-methanoindene substituted in one of the 5 and 6 positions with crotonoyloxy; or 3a,4,5,6,7,7a-hexahydro-4,7- methanoindene substituted in one of the 5 and 6 positions with senecioyloxy; and 5-acrylyloxy-2,3,3a,4,5,6,7,7a-octahydro-4,7-methanoindene; S-(alpha, beta-dimethyl acrylyloxy) 2,3,3a,4,5,6,7,7a octahydro 4,7 methanoindene; 5 crotonoyloxy 2,3,3a,4,5,6,7,7a-octahydro- 4,7-methanoindene; or S-seneciolyloxy-Z,3,3a,4,5,6,7,7aoctahydro-4,7-methanoindene.

When the substituted 4,7-methanoindenes of this invention are prepared by reacting an acid reactant, that is where X of the above Formula 111 is hydrogen, with the corresponding hydroxy substituted methanoindene, which is the preferred preparational method of this invention, the reaction may be elfected as follows: The reaction is conducted under esterification conditions which are not critical and may be varied over a wide range. Generally, the temperature used in combination with atmospheric pressure may range from about 30 C. up to the reflux temperature of the reaction mixture with the refluxing temperatures being preferred. Although the reaction may be conducted in the absence of a solvent, the results are generaly improved when a solvent is used and a suitable solvent for such purpose comprises an aromatic hydrocarbon such as, for example, benzene or toluene. When a solvent is employed to facilitate the reaction, the amount used is not important and generally a quantity of solvent approximately equal in weight to the total weight of the acid reactant and the hydroxy substituted methanoindene may be satisfactorily utilized. In effecting the reaction, it is necessary that an acid acting catalyst be used, and such catalyst may comprise any of the well known esterification catalyst such as for example, sulfuric acid, methane sulfonic acid, or sulfonic acid resins. The amount of catalyst used in the reaction may be a catalytic amount usually employed in such esterification reactions which may range from about 0.01 to 20 weight percent of the combined weight of the reactants depending upon the particular catalyst used and the reaction rate desired. The ratio of the reactants used is not critical and generally stoichiometric ratio of about one mol of the acid reactant per mol of the hydroxy methanoindene may be suitably utilized in most instances. The results, however, are frequently improved by using an excess of the acid reactant. In carrying out the reaction, which preferably is effected in a batch-type operation, the desired acid reactant, the desired hydroxy substituted methanoindene, a suitable acid acting catalyst and a solvent, if one is used, are charged to an appropriate reaction vessel equipped heating and stirring means. The temperature of the mixture is then raised to the above described range and maintained thereat until the reaction is complete; a period usually requiring from about 5 to 25 hours. The reaction mixture is then neutralized and fractionated to recover the desired substituted methanoindene.

When the substituted 4,7-methanoindenes of the in vention are prepared by reacting an ester reactant, that is where X of the above Formula III is an alkyl group, with the corresponding hydroxy substituted methanoindene, the reaction may be effected as follows: The reac tion is conducted under transesterification conditions which are not critical and may be varied over a wide range. Generally, the temperature used in combination with atmospheric pressure may range from about 50 C. up to about the normal boiling point of the ester reactant. Advantageously, however, the reaction temperature is maintained at the reflux temperature of the reaction mixture throughout the reaction. The ratio of the reactants used is not important and generally a stoichiometric ratio of about one mol of ester reactant per mol of the hydroxy substituted methanoindene may be suitably utilized in most instances. The formation of the product, however, is usually favored by utilizing an excess of the ester reactant of up to about 300 percent of theory. In efiecting the reaction, it is necessary that a transesterification catalyst be present in the reaction mixture, and such a catalyst may comprise any one of the frequently used transesterification catalysts, such as, for example, sodium methylate or an aluminum alkoxide such as aluminum isopropylate. The quantity of the transesterification catalyst used in the reaction may be a catalytic amount which varies depending upon the particular catalyst and the reaction rate desired. Generally, a quantity of catalyst ranging from about 0.01 to 50 weight percent of the combined Weight of the reactants is suitable for most purposes with from about 0.1 to 5 percent being preferred. In carrying out the reaction, which is advantageously efl'ected in a batch-type operation, the desired ester reactant and the desired hydroxy substituted methanoindene are charged together with an appropriate transesterification catalyst to a suitable reaction vessel, heated to the above described temperature range and maintained thereat until the reaction is complete; a period usually ranging from about 5 to 20 hours. A preferred and highly advantageous manner of effecting the reaction, however, is to continuously remove the alkyl alcohol formed in the reaction from the reaction mixture as it forms, such as by distillation, in order to drive the reaction to completion. When the reaction is complete, the catalyst may be neutralized and any remaining alkyl alcohol and any excess ester reactant distilled from the mixture. The remaining product mixture may then be Washed and the product extracted therefrom with an organic solvent. The substituted methanoindene product may then be separated from the solvent by fractionation to recover a highly pure product.

When substituted 4,7-methanoindenes of this invention are prepared by reacting an acid halide reactant, that is where Y of the above Formula IV is a halogen, with the corresponding hydroxy substituted methanoindene, the reaction may be elfected as follows: The conditions used in conducting the reaction are not critical and may be varied over a wide range. Generally, the temperature used in combination with atmospheric pressure may range from about 5 C. to C. with a temperature of from about 0 C. to 20 C. being preferred. The reaction is preferably effected in the presence of a basic material to act as an acid acceptor for the acid formed during the reaction. Acid acceptors which may be used include such basic materials as pyridine or a trialkyl amine such as tributylamine. While it is not essential that the reaction be effected in the presence of a solvent, the results are generally improved when a solvent is utilized. Solvents which may be used include aromatic hydrocarbons such as toluene or benzene. Advantageously, one of the aforementioned acid acceptors may be used in a dual role as both an acid acceptor and a solvent. When an acid acceptor is used as the solvent, the quantity used may be widely varied with an amount approximately equal to the weight of the reactants being satisfactorily used in most instances. The ratio of reactants is not important and generally a stoichiometric ratio of about one mole of the acid halide reactant per mole of the hydroxy substituted methanoindene is suitably utilized in most instances. The results, however, are frequently improved by using an excess of the hydroxy substituted methanoindene. In carrying out the reaction, which is advantageously effected in a batch-type operation, the desired acid halide reactant and the desired hydroxy substutitued methanoindene are charged together with a solvent, if one is used, and acid acceptor to a suitable reaction vessel. The mixture is then heated or cooled to the above described temperature range and maintained thereat until the reaction is complete; a period usually ranging from about two to 24 hours. At the completion of the reaction, the substituted methanoindene product may be recovered from the reaction mixture after removal of the acid acceptor by washing or by fractional distillation.

As hereinbefore indicated the highly pleasant odoriferous nature of the novel compounds of this invention render them highly valuable as perfume ingredients. The odor and odor characteristics of the different compounds embraced within this invention differ widely, however, and of the different compounds the most remarkable odors both from the standpoint of their pleasing nature and from their odor classification are possessed by the hexahydro-4,7-methanoindenes substituted in one of the and 6 positions with a senecioyloxy, a crotonoyloxy or an alpha, beta-dimethyl acrylyloxy substituent. These compounds, with various modifications, have intense woody odors which are highly valued in perfumery.

The compounds of this invention, either individually or in admixture, are used in perfumes as the olfactory ingredients thereof and thus create novel perfume compositions. As used herein, the term perfume means a mixture of organic compounds including, for example, alcohols, aldehydes, ketones, esters, and frequently also hydrocarbons which are combined in fixed proportions so that the odors of the individual compounds combine to produce a harmonious fragrance. The quantity of the compounds of this invention utilized in perfumes may vary within a Wide range and depends upon the particular compound used and the particular type of perfume being created. For example, in the preparation of Muguettype perfumes, the quantity of the substituted methanoindene used may range from about 0.01 to 25 percent of the total weight of the perfume with a quantity of about 2 to 5 percent by weight being preferred.

The perfume compositions of this invention having the substituted 4,7-methanoindenes as olfactory ingredients may be used per se or incorporated into items such as cosmetic creams, soaps, synthetic detergents, talcum powders or other toilet goods such as shampoos to produce products having the desirable commercial fragrance properties.

The following examples are given to illustrate the compounds of this invention, the preparational process therefor and perfume compositions containing the compounds as olfactory ingredients. These examples are not, however, intended to limit the generally broad scope of the present invention in strict accordance therewith.

EXAMPLE I 3a,4,5,6,7,7a-hexahydro-4,7-methanoindene substituted in one of the 5 and 6 positions with senecioyloxy was prepared according to the process of this invention by the following procedure:

About 50 grams (0.5 mole) of senecioic acid, about 130 grams of toluene, about 50 grams (0.33 mole) of 3a,4,5,6,7,7a-hexahydro-4,7-methanoindene substituted in one of the 5 and 6 positions with hydroxy and about 0.5 milliliter of concentrated sulfuric acid were charged to a reaction flask equipped with heating and stirring means and an overhead water trap. With stirring the reaction mixture was brought to reflux (120 C.) and about 1.5 milliliters of methane sulfonic acid were added to supplement the sulfuric acid catalyst present. The refluxing was continued for about 13 hours during which time about 6 grams of water were collected in the trap. The reaction mixture was then cooled, washed with a sodium bicarbonate solution followed by several water washings and then dried over sodium sulfate. The toluene solvent was then stripped from the mixture and the remaining mixture was then subjected to vacuum fractionation to recover the product distilling at 130 C. at 1.1 mm. of mercury pressure and having a refractive index of n- 1.5148 to 1.5152.

EXAMPLE II 5-senecioyloxy-2,3,3a,4,5,6,7,7a octahydro-4,7-methanoindene was prepared according to the process of this invention by the following procedure:

About 37 grams (0.37 mole) of senecioic acid, about 150 grams of toluene, about 51 grams (0.33 mole) of 5-hydroxy-2,3,3a,4,5,6,7,7a-octahydromethanoindene and about 1 milliliter of methane sulfonic acid were charged to a reaction flask equipped with heating and stirring means and an overhead water trap. With stirring the reaction rnixture was brought to reflux temperature (120 C.), and maintained thereat for about 14.5 hours during which time about 5.4 cubic centimeters of water were collected in the trap. The reaction mixture was then cooled, washed with a sodium bicarbonate solution followed by several water washings and then dried over calcium chloride. The toluene solvent was then stripped from the mixture and the remaining mixture was then subjected to vacuum fractionation to recover the product distilling at 117 C. at 0.7 mm. of mercury pressure and having a refractive index of n; 1.5050 to 1.5053.

EXAMPLE III 3a,4,5,6,7,7a-hexahydro-4,7-methanoindene substituted in one of the 5 and 6 positions with alpha, beta-dimethyl acrylyloxy was prepared according to the process of this invention by the following procedure:

About 75 grams (0.5 mole) of 3a,4,5,6,7,7a-hexahydro-4,7-methanoindene substituted in one of the 5 and 6 positions with hydroxy, about 68.5 grams (0.6 mole) of the methyl ester of alpha, beta-dimethyl acrylic acid (tiglic acid) and about 0.25 gram of sodium methylate were charged to a reaction flask equipped overhead with a short packed column with a reflux splitter and heating and mixing means. The mixture was heated to reflux temperature (about 171 C.) and after about 2 hours, 0.4 gram more of the sodium methylate were added and the refluxing continued for about another 3 hours. During this period about 13.3 grams of methyl alcohol were collected as distillate. The reaction flask was then subjected to vacuum to remove the remaining methyl ester of tiglic acid and thereafter cooled to about 25 C. About grams of benzene were added and the resulting solution was then washed first with about 50 grams of a 2 percent acetic acid solution and then with water followed by drying over magnesium sulfate. The benzene was stripped from the dried mixture, and the remaining mixture fractionated under vacuum to recover the product distilling at 130 C. at 1.5 mm. of mercury pressure and having a refractive index of n 1.5097 to 1.5112.

EXAMPLE IV 3a,4,5,6,7,7a-hexahydro-4,7-methanoindene substituted in one of the 5 and 6 positions with crotonoyloxy was prepared according to the process of this invention by the following procedure:

About 112.5 grams (0.75 mole) of 3a,4,5,6,7,7a-hexahydromethanoindene substituted in one of the 5 and 6 positions with hydroxy, about 125 grams (1.25 mole) of the methyl ester of crotonic acid and about 1 gram of sodium methylate were charged to a reaction flask equipped overhead with a short packed column with a reflux splitter and heating and mixing means. The mixture was heated to reflux temperature (about C.) and maintained thereat for about 5 hours. During this period about 29.7 grams of methyl alcohol were collected as distillate. The reaction mixture was then cooled to about 25 C. and about 65 grams of hexane added. The resulting mixture was then washed with water and a salt solution and then dried over magnesium sulfate. The hexane solvent was stripped from the dried mixture and the remaining mixture fractionated under vacuum to recover the product distilling at 148 to 152 C. at 6 mm. of mercury pressure and having a refractive index 11 1.5111 to 1.5118.

EXAMPLE V senecioyloxy 2,3,3a,4,5,6,7,7a octahydro 4,7 methanoindene is prepared according to the process of this invention by the following procedure:

About 76 grams (0.5 mole) of 5-hydroxy-2,3,3a,4,5,6, 7,7a-octahydro4,7-methanoindene and about 500 grams of pyridine are charged to the reaction flask equipped with cooling/ heating and mixing means. With mixing and with the temperature maintained at about 5 C, about 64.9 grams (0.55 mole) of senecioyl chloride are added to the mixture. The mixture is then maintained at about 28 C. for about 15 hours. The pyridine is then removed from the reaction mixture by extracting with hexane and washing with water The remaining mixture is then fractionally distilled to recover the desired product.

EXAMPLE VI A perfume of the following composition having a Muguet character Was made using a compound of this invention as an olfactory ingredient:

Component: Part by weight 3a,4,5,6,7,7a-hexahydro-4,7-methanoindene sub tituted in one of the 5 and 6 positions with 8 Benzyl salicylate 0.5 Citronellyl formate 0.8

I claim as my invention:

1. A perfume composition comprising as an olfactory ingredient thereof from about 0.01% to 25% by Weight of said composition of at least one compound selected from the group consisting of 3a,4,5,6,7,7a-hexahydro-4,7- methanoindene and 2,3,3a,4,5,6,7,7a-octahydro-4,7-methanoindene which is substituted in one of the 5 and 6 positions with a substituent of the formula:

wherein R R R taken independently of each other is a member selected from the group consisting of hydrogen, methyl and ethyl and a perfume carrier comprising a mixture of organic compounds selected from the group consisting of alcohols, aldehydes, ketones, esters and hydrocarbons.

2. The perfume composition according to claim 1 wherein the substituent of the compound as the olfactory ingredient is senecioyloxy.

3. The perfume composition according to claim 1 wherein the substituent of the compound as the olfactory ingredient is crotonoyloxy.

4. The perfume composition according to claim 1 wherein the substituent of the compound as the olfactory i11- gredient is alpha, beta-dimethyl acrylyloxy.

References Cited UNITED STATES PATENTS 3,065,192 11/1962 Dimler et a1. 260486X ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner US. Cl. X.R. 

